CN102459150B - Process for preparing alkylalkanolamines - Google Patents
Process for preparing alkylalkanolamines Download PDFInfo
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- CN102459150B CN102459150B CN201080037490.2A CN201080037490A CN102459150B CN 102459150 B CN102459150 B CN 102459150B CN 201080037490 A CN201080037490 A CN 201080037490A CN 102459150 B CN102459150 B CN 102459150B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
- C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
- C07C215/08—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with only one hydroxy group and one amino group bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
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Abstract
The present invention relates to a process for preparing alkylalkanolamines, comprising the reaction of a carbonyl-based compound with a hydroxylalkylamine, in the presence of hydrogen and a catalyst.
Description
The present invention relates to the method for the synthesis of alkyl alkanolamine (being called AAA later), allow the ameliorative way (especially at industrial scale) obtaining high purity alkyl alkanolamine in the starting material situation not using epoxide-type with high yield especially.
AAA, especially alkyl ethanol amine, be intermediate compound important in chemical industry and in pharmaceutical industry, in these industry, they can be used as dispersion agent, emulsifying agent or tensio-active agent or be used in the synthesis of activeconstituents.Just to mentioning modal application, they are also used as the neutralizing agent in aqueous coating, or as the corrosion inhibitor in lubricant or hydraulic fluids.
According to normally used preparation method, AAA, especially alkyl ethanol amine, carry out reaction by making uncle or secondary amine and epoxide (respectively oxyethane) obtain as pointed in following reaction:
。
These reactions are such as described in patent application FR 2 251 545 (BASF) or FR 2 387 212 (Bayer).
According to this reaction process, therefore secondary amine produce N, N-dialkylethanolamines, and primary amine produces N-alkyl ethanol amine or N-alkyldiethanolamine according to the stoichiometric ratio used.
But especially when primary amine, this reaction produces the mixture of alkyl monoethanolamine and alkyldiethanolamine the most usually, they are difficult to according to the character of its alkyl be separated sometimes.
And this preparation method produces byproduct, and it is the compound of the polyaddition from used epoxide, such as, when using oxyethane:
。
It is further well known that produce AAA, especially alkyl ethanol amine by this operating method, it becomes coloured during distilling and/or between the shelf lives.This painted owing to there is the unsaturated impurity of conjugation and/or carbonylation derivant and can proving that for some application be particularly troublesome, especially in coating (white basic material).
Describe different treatment processs to limit this alkyl ethanol amine coloring problem.
In these problems, can mention at patent and patent application US 2004/0110988 (Air Products), US 6291715 (BASF), describe in EP 632013 (Union Carbide) and EP 477593 (Atochem) those, only to mention some in them, carry out large quantity research to attempt solving this coloring problem to show.
Especially, in order to suppress to bring painted compound, a technical scheme is with reductive agent (as hydrogen, NaBH
4etc.) processing reaction crude product, or the AAA distilled in advance.Therefore this technical scheme requires additional processing reacting coarse product, and this provable energy consuming is expensive and yield declines.
Therefore the needs to the method for the synthesis of AAA are also had now, it can easily industrialization, has excellent yield, can exempt and use dangerous or unworkable starting material, only produce with it and seldom or not produce byproduct, cause the byproduct that AAA is painted especially.
These targets fully or at least in part reach by means of the present invention, and details of the present invention describes in detail in the following description.
Therefore, according to first aspect, theme of the present invention comprises a kind of direct synthesis method, it avoids using the compound with epoxy-functional, oxyethane (it is extremely inflammable and poisonous liquefied gas) especially, described direct synthesis method produces highly purified AAA after the distillation, especially alkyl ethanol amine, it is colourless and stable storing, need not any additional specific purification process.
More specifically, the present invention relates to the method for the preparation of formula (A) alkyl alkanolamine:
Wherein:
R
1represent hydroxyalkyl, wherein moieties is straight chain and comprises two carbon atoms;
R
2be selected from hydrogen atom and comprise two carbon atoms and the straight chained alkyl replaced with one or more hydroxyl (-OH);
R and R', can be same or different, eachly be selected from hydrogen atom, alkyl, hydroxyalkyl, alkoxyl group, alkylamino, dialkyl amido, alkoxyalkyl, wherein alkyl comprises 1-10, preferably 1-6 carbon atom based on chain that is linear or branched hydrocarbon, with the cycloalkyl comprising 3-9 carbon atom, qualifications is that R and R' eachly side by side can not represent hydrogen atom;
Or
R with R' jointly formed together with carrying their carbon atom saturated or completely or partially undersaturated, single-, two-or polycyclic moiety, it optionally comprises one or more heteroatoms being selected from oxygen, sulphur and nitrogen,
Described method is included in the step making formula (1) carbonyl containing compound reduction amination when hydrogen and catalyzer exist with formula (2) hydroxyalkyl amine:
Wherein R, R', R
1and R
2as defined above.
At this specification sheets, unless otherwise stated, understand as follows:
alkyl: linear or branching, be optionally substituted, comprise 1-10, the preferably group based on hydrocarbon of 1-6 carbon atom, or comprise 3-9, the preferably group based on cyclic hydrocarbon of 5-9 carbon atom;
single-, two-or polycyclic moiety: saturated or completely or partially undersaturated, the list that is optionally substituted-, two-or polycyclic moiety, it optionally comprises one or more heteroatoms being selected from oxygen, sulphur and nitrogen, and ring members (sommets) number is 3-12.Preferably, described group is monocycle and comprises 3-9 ring members, and preferably it comprises 5,6 or 7 ring memberses.
In a preferred embodiment of the invention, understand as follows:
alkyl: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, neo-pentyl, 1,2-dimethyl propyl, n-hexyl, isohexyl, the second month in a season-hexyl, cyclopentyl-methyl, n-heptyl, different heptyl, cyclohexyl methyl, n-octyl, iso-octyl, 2-ethylhexyl and positive decyl, preferable methyl, ethyl or propyl group;
hydroxyalkyl: methylol, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxyl-n-propyl group, 2-hydroxyl-n-propyl group, 3-hydroxyl-n-propyl group and 1-(methylol) ethyl, preferred hydroxyethyl, hydroxypropyl, more preferably 2-hydroxyethyl, 2-hydroxyl-n-propyl group;
alkylamino: methylamino, 2-ethylamino, amino, the n-propyl group-3-amino of amino, the n-propyl group-2-of 1,1-dimethyl ethyl-2-, normal-butyl-4-amino, n-pentyl-5-amino, comprise arylamino, it is optionally substituted, such as phenyl amino;
dialkyl amido: dimethylamino, two (2-ethyl) is amino, two (1, 1-dimethyl ethyl)-2-amino, two (n-propyl group)-2-is amino, two (n-propyl group)-3-is amino, two (normal-butyl)-4-is amino, two (n-pentyl)-5-is amino, N-(2-ethyl)-N-methylamino, N-(1, 1-dimethyl ethyl)-N-methyl-2-amino, N-(n-propyl group)-N-methyl-2-amino, N-(n-propyl group)-N-methyl-3-is amino, N-(normal-butyl)-N-methyl-4-is amino, N-(n-pentyl)-N-methyl-5-is amino, N-(2-ethyl)-N-ethylamino, N-(1, 1-dimethyl ethyl)-N-ethyl-2-amino, N-(n-propyl group)-N-ethyl-2-is amino, N-(n-propyl group)-N-ethyl-3-is amino, N-(normal-butyl)-N-ethyl-4-is amino and N-(n-pentyl)-N-ethyl-5-is amino, comprise ammonia diaryl base, it is optionally substituted, such as diphenyl amino,
cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group, preferred cyclopentyl and cyclohexyl.
In formula (1) compound, be preferably selected from following those:
ketone: acetone, pyruvic alcohol, methyl ethyl ketone (MEK), methyl propyl ketone, methyl isopropyl Ketone, methyl iso-butyl ketone (MIBK), metacetone, diisobutyl ketone, Tetralone an intermediate of Sertraline, methyl phenyl ketone, p-methyl aceto phenone, p-methoxy-acetophenone, meta-methoxy methyl phenyl ketone, 2-aminoacetophenone, 1-phenyl-3-butanone, cyclobutanone, cyclopentanone, pimelinketone, benzophenone, 2-Uvinul A Plus, 3-Uvinul A Plus, 4-Uvinul A Plus, 3,3,5-trimethylcyclohexanone, 2,6-dimethylcyclohexanon, suberone and cyclododecanone;
aldehyde: acetaldehyde, propionic aldehyde, butyraldehyde-n, isobutyric aldehyde, pivalyl aldehyde, valeral, n-hexyl aldehyde, 2-ethyl hexanal, enanthaldehyde, enanthaldehyde especially, octanal, especially n-octaldehyde, the undecyl aldehyde, phenyl aldehyde, aubepine, p-tolualdehyde, phenylacetic aldehyde, hydroxy pivalin aldehyde and furfural.
In formula (2) compound, be preferably selected from those of (uncle or secondary) hydroxyalkyl amine or two (hydroxyalkyl) amine, be selected from monoethanolamine and diethanolamine those especially.
Method according to the present invention comprises the reduction amination of aldehydes or ketones monohydroxyalkylamine or dihydroxyalkylamine, does not preferably add organic solvent, and it operates with heterogeneous catalyst (catalyzer agitated bed) according to interval or semicontinuous method.
According to method of the present invention also preferably with close to stoichiometric carbonyl containing compound/amine mol ratio (or at hereinafter RM of the present disclosure), more preferably carry out with the carbonyl containing compound slightly excessive relative to amine.
Therefore, according to a preferred embodiment according to the inventive method, RM is advantageously 0.9-1.8, preferably 1.0-1.5 (for uncle or the monoalkylation of secondary amine), be advantageously 1.8-3.6 with RM, preferably 2.0-3.0, more preferably 2.1-2.5 (di for primary amine).
This method from monoethanolamine (MEoA) and diethanolamine (DEoA), according to operational condition, can prepare different alkyl alkanolamine, as following provide as an example but nonrestrictive synthetic schemes with pointing out:
。
Can be so the Non-limiting examples of alkyl alkanolamine that obtains of method according to the present invention from methyl ethyl ketone and prepare from monoethanolamine N-the second month in a season-butylethanolamine (sBAE), from enanthaldehyde and N-(n-heptyl) diethanolamine (C7DEoA) prepared from diethanolamine (DEoA), from acetone and N-(sec.-propyl) thanomin prepared from monoethanolamine (MEoA), from butyraldehyde-n and N-(normal-butyl) diethanolamine prepared from diethanolamine (DEoA), with from butyraldehyde-n and the N for preparing from monoethanolamine (MEoA), N'-bis-(normal-butyl) thanomin.
The hydrogenation catalyst that can be used in the inventive method can be the hydrogenation catalyst of the known any type of this skilled artisan in hydrogenating organic compounds field.Preferably use any type catalyst of the catalytic hydrogenation be often used in multiphase medium.
The limiting examples of this catalyzer can be selected from the hydrogenation catalyst of the metal based on the 8th, 9,10 and 11 races from the periodic table of elements (IUPAC), be preferably based on the Raney catalyst of Ni, Co or Cu, Pd (Pd/C type) and copper chromite, more particularly Raney nickel type catalyst.
Can in the catalyzer that obtains of business what be suitable for that method according to the present invention needs, as limiting examples, nickel catalyzator BLM 112 W (Evonik) can be mentioned, Amperkat SK-Ni Fe Cr 4546 (H.C.Starck) and Cu-1955 (BASF Catalysts).
Can advantageously, even desirably, this catalyzer of pre-treatment use this catalyzer in reductive amination process according to the present invention before, described pre-treatment comprises catalyzer described in pre-reduction under hydrogen stream in advance.This is normally when catalyzer is with situation when its oxidised form (when the copper chromite of Cu-1955P type) or the sale of only partial reduction form.
When for when carrying out reduction temperature lower than described catalyzer of temperature of reaction that reduction amination according to the present invention limits, this pre-treatment is recommended, or even required.
Method according to the present invention is particularly suitable for preparing alkyl alkanolamine with interval or semicontinuous state on industrial level, equipment and the unit affinity being generally used for hydrogenation.In fact, method according to the present invention is carried out under hydrogen-pressure (usually between normal atmosphere to 150 clings to, preferably 5 bar-80 cling to, and particularly 10 bar-50 cling to).
This temperature of reaction can change according to the character of the catalyzer of raw-material character and use to a great extent, and usually in the scope of 20 DEG C-180 DEG C.Such as, this temperature of reaction is preferably 40 DEG C-100 DEG C (using Raney nickel type catalyst), is preferably 120 DEG C-160 DEG C (use copper chromites).
As noted before, the azanol of formula 2, monoethanolamine (MEoA) and diethanolamine (DEoA) use with anhydrous form or with the aqueous solution form of selling especially.Due to the fusing point of anhydrous DEoA, the moisture form of this sale, those needs for method according to the present invention such as with 85% titre are preferred.
Can carry out with interval or semicontinuous state according to method of the present invention.But when formula (1) carbonyl containing compound is aldehyde, the method advantageously carries out (along with the consumption of aldehyde adds aldehyde) to control selectivity with semicontinuous state.
Preferably, method according to the present invention, when solvent-free, is carried out during organic solvent-free especially, understanding be that the amine of formula (2) can use in the aqueous solution as noted above.
At the end of reductive amination process, after settled catalyst and separating liquid crude product, catalyzer can be used further to another reductive amination process as it is, namely can carry out on same catalyzer tailing according to another reductive amination process of the present invention.
Due to method of the present invention, do not need to use reductive agent (as hydrogen, NaBH
4etc.) process this reacting coarse product to suppress to bring painted compound, as it is being generally used for preparing the situation in synthesis that alkyl alkanolamine carries out (use especially oxyethane those).
Therefore, method according to the present invention has the advantage can exempting reduction treatment.This reacting coarse product is therefore directly in distillation reaction under reduced pressure, and make it possible to obtain highly purified colourless alkyl alkanolamine, it is painted keeps stable between the shelf lives.
For example, the sBAE's that obtains of method according to the present invention is painted lower than 3 Pt-Co units.After storing 18 months at ambient temperature in glass packaging (lucifuge) or HDPE packaging, or store December in steel drum after, keep colourless (lower than 3 Pt-Co units).
This is painted to use metric measurement by Dr Lange LTM1 colorimeter according to ISO 6271-2:2004 (platinum cobalt colour scale) standard; Painted therefore with Pt-Co unit representation (being equivalent to also normally used Hazen or APHA unit).
Therefore make it possible to be produced as colourless or that there is few color AAA according to the method for the preparation of AAA of the present invention, but due to their unstable, the AAA that Vehicles Collected from Market is sold is usually with about 50Hazen, and even the specification of 100 Hazen is sold.
The present invention is described by embodiment subsequently now, and this embodiment is not restrictive in scope of the present invention (this scope is limited by accessory claim).
the synthesis of embodiment 1:N-(sec-butyl) thanomin (sBAE)
N-(sec-butyl) thanomin is prepared from methyl ethyl ketone with from monoethanolamine (MEoA) according to following reaction process:
。
The main side reaction that can occur between this reaction period is following:
A) make methyl ethyl ketone hydrogenation to produce methylethyl methyl alcohol (B2):
B) make monoethanolamine disproportionation to produce diethanolamine (DEoA) and ammonia:
C) by using ammonia to make methyl ethyl ketone reduction amination form sec-butylamine (B2A):
D) for the reaction from condensation of methyl ethyl ketone, preparation EAK (EAK) then EAC (ethyl pentyl group methyl alcohol):
E) di of monoethanolamine corresponds to the reaction of sBAE and methyl ethyl ketone:
The methyl ethyl ketone (MEK) (supplier Arkema) used has the standard industry purity of 99.9%.
The monoethanolamine (MEoA) (supplier: BASF) used with its anhydrous form has the purity being greater than 99.7%.
The catalyzer used in this embodiment, Cu 1955 P (supplier: BASF Catalysts) is packaged in the copper chromite in solubilized pouch.
detailed method of operation
Test be equipped with stirring and gas/liquid dispersion system, for use steam heating and use water-cooled chuck, for the inside serpentine tube of additional cooling reaction medium and 65 L autoclaves of pressure and temperature setter in carry out.
step is a): the preliminary reduction of Cu 1955P
Cu 1955P catalyzer (in " SecuBag " type plastics bag 2.3 kilograms) is fed in autoclave.Introduce 34.8 kg MEK.This autoclave uses nitrogen to purge, and then injects nitrogen to provide the pressure of about 2 bar at autoclave.
Inject hydrogen until reach the pressure of 13 bar at ambient temperature.Then start to stir and heating high-pressure still.When temperature reaches 80 DEG C, pressure is made to be increased to 20 bar by injecting hydrogen.
The reduction of catalyzer is 125 DEG C of beginnings.Hydrogen flow rate is limited in 5 Nm
3/ h.Then Pressure Drop is made to be low to moderate 9 bar.At the end of reduction, pressure is increased to 28 bar again.Under 28 bar hydrogen, this reaction medium is kept again 30 minutes at 130 DEG C.Stir in stopping and after settled catalyst, make the sec-butyl alcohol draining of formation.
step b): synthesis sBAE
Five continuously testeds (test A to E) are carried out to the catalyzer tailing produced in the step above.Charging 23 kg MEK is about 18.4 kg MEoA then.Then hydrogen is injected until reach the pressure of 15 bar.
Then start to stir and heating high-pressure still.Hydrogenation starts 80 DEG C time.Little by little but to maintain 5 Nm
3the method of the instantaneous peak flow of hydrogen of/h improves temperature.
For test A, hydrogenation was carried out in 5 hours 30 minutes at 130 DEG C of temperature, under 28 bar pressures.
For test b to D, hydrogenation is carried out 3 hours 30 minutes the top temperature of 130 DEG C and continues 1 hour 30 minutes at 135 DEG C.
For test E, hydrogenation was directly carried out at the temperature of 135 DEG C in 5 hours 30 minutes.
For difference test A to E, at the end of hydrogenation, make this reaction medium be cooled to 90 DEG C and then stop stirring.In addition, at hydrogen exhaust until after 1 bar, make catalyst sedimentation at least 2 hours, then make this reacting coarse product draining.
result:
The transformation efficiency of each acquisition, selectivity and yield in these five tests are concentrated in the following table 1.
The transformation efficiency of MEoA is 98.6%-99.8%, simultaneously in the face of the sBAE selectivity of MEoA is 97.5%-98.2%, is therefore about 96%-98% relative to the thick molar yield of sBAE of the initial MEoA used.
table 1
Weight in average composition (passing through gas chromatography determination) of the crude product of these five operations provides in table 2 below:
table 2
distillation:
The mixture of aforementioned five crude products of 206 kg is used to carry out single distillation procedure on the tower with about 20 theoretical stages.
Can light product be extracted in atmospheric predistillation step, as MEK and B2 of remnants, and most of water.EAK and EAC forming azeotrope with water also mainly extracts in this overhead fraction.
Temperature at tower top: 77 DEG C-99 DEG C;
Temperature in generator: 104 DEG C-155 DEG C;
In reflux ratio ~ 1 of top of tower.
Overhead product is two-phase.After decant goes out this light product cut, reclaim 22.7 kg and there is aqueous phase (F1 aq.) and 6.0 kg organic phases (F2 aq.) that to point out in following table 3 to form.
table 3
Then distillation is under reduced pressure continued.At the top of tower removing residual water then by extracting recovery ' pure ' sBAE at the effluent of tower At The Height of about 70%.Draw sBAE with high temperature, short time type of heating (en pasteuris é) and remaining MEoA can be concentrated at the top of this tower.
Pressure at tower top: 60 millibars-70 millibars;
Temperature at tower top: 34 DEG C-100 DEG C;
The temperature of height is being drawn: 101 DEG C-103 DEG C by effluent;
Temperature in generator: 110 DEG C-128 DEG C;
In reflux ratio ~ 10 of tower top;
Reflux ratio ~ the 1-2 of height is drawn at effluent.
Reclaim 12.8kg cut F2 thus, and 137.7kg has ' pure ' sBAE of 99.9% purity, it accounts for 82.1% of the sBAE be present in generator initial charge.
Consider " hold-up " of this tower, distillation yield is about 85%.
The high purity sBAE of preparation like this keeps almost colourless (painted lower than 3 Pt-Co units) after storing more than 18 months.
the synthesis of embodiment 2:N-(n-heptyl) diethanolamine (C7DEoA)
N-heptyl diethanolamine is prepared from enanthaldehyde and diethanolamine (DEoA).
In 2 L stainless steel Sotelem reactors, Amperkat SK-Ni Fe Cr 4546 Ni/ Raney catalyst (supplier H.C.Starck) is used to carry out three synthetic operations (K, L, M) continuously to same catalyst tailing.
tested K
After autoclave (there is 95g water) charging 50g Amperkat catalyzer, then purge this autoclave with nitrogen, use pump to introduce 391.3g 85%DEoA (i.e. the DEoA of clean 332.6 g, corresponding to 3.16 mol).
Then inject hydrogen until reach the pressure of 15 bar, then under agitation heat these mixtures at 90 DEG C and hydrogen pressure is adjusted to 28 bar.
Then use pump to introduce enanthaldehyde (supplier Arkema, purity 97%) with 350 g/h flow velocitys, inject hydrogen to keep the pressure of 28 bar simultaneously, make this reaction medium temperature maintain 90 DEG C simultaneously.
After introducing 487.5g enanthaldehyde (i.e. 4.14 mol), 90 DEG C and under 28 bar hydrogen this reaction medium of maintenance stirring 30 minutes again.
Then stop stirring, at hydrogen exhaust until 1 bar, and make catalyst sedimentation at least two hours.
Then reacting coarse product supernatant liquor (to remove possible catalyst fines) is bled off by strainer.So reclaimed the thick C7DEoA of 866.6 g, show do not have remaining enanthaldehyde completely by its weight composition (table 4) of gas chromatography determination, the enanthaldehyde major part excessive relative to DEoA is converted into n-Heptyl alcohol.
test L
According to the operating method identical with tested K, but by directly to catalyzer tailing charging 395 g of the tested K remained in autoclave 85%DEoA (i.e. the DEoA of clean 335.8 g, corresponding to 3.19 mol) and measure the enanthaldehyde of (3.67 mol) by injection 432.3 g within 1 hour 15 minutes periods and carry out this test.At the end of this reaction, so reclaim the thick C7DEoA of 833.3 g, pointed out in table 4 by its weight composition of gas chromatography determination.
test M
According to the operating method identical with tested K, but by directly to catalyzer tailing charging 401.1 g of the test L remained in autoclave 85%DEoA (i.e. the DEoA of clean 340.9 g, corresponding to 3.24 mol) and measure the enanthaldehyde of (3.68 mol) by injection 432.7 g within 1 hour 15 minutes periods and carry out this test.At the end of this reaction, so reclaim the thick C7DEoA of 837.3 g, pointed out in table 4 by its weight composition of gas chromatography determination.
table 4
After reacting coarse product on mixing these three kinds, the Sovirel distillation column filling up Multiknit weighting material with 1m height carries out purification process.
After the thick C7DEoA mixture of generator charging 2113 g of this tower, then the latter to be used in generator the top temperature of 150 DEG C at the end of concentrated alcohol and water in heptan (tower top temperature: 96-98 DEG C) and to consume water by extracting at normal atmosphere azeotropic and concentrate under 50 millibars of pressure.
Reclaim the organic fraction that 243.2 g comprise 86.2% enanthol, 5.2% water and 7.6% organic impurity thus, then 312.7 g comprise the aqueous phase of 99.5% water, 0.25% enanthol and 0.25% organic impurity.
Consisting of of tailing (1509.3g) is after concentration as follows:
Enanthol: 0.09%;
· DEoA：1.86%；
Other organic impurity: 1.60%;
Water: 0.06%;
· C7DEoA：96.4%。
By continuing this tailing in identical device lower than the fractionation under the pressure of 1 millibar, with after being separated the overhead fraction being rich in DEoA, obtain the C7DEoA of 1358 g distillations in 137.0 DEG C of-137.5 DEG C of tower top temperatures and the top temperature being used in generator 180 DEG C.
The purity of the C7DEoA of this distillation is 98.7%, and simultaneously the residual content of DEoA is 0.05%, and water-content is 0.02% and painted lower than 3 Pt-Co units.
Use the distillation yield of 89.5%, therefore total molar yield of the C7DEoA of distillation is the DEoA about 85% relative to initial use.
Store 6 months under envrionment temperature and lucifuge in glass flask after, the painted maintenance of the C7DEoA of so preparation is metastable, because it equals only 5 Pt-Co units.
The following example, according to similar operating method, is implemented as changed with pointing out by making starting material.
embodiment 3: synthesize N-(sec.-propyl) thanomin (IPAE) from acetone and MEoA according to interrupter method (sBAE type)
Using the acetone/MEoA mol ratio of 1.05, is the Cu 1955P catalyzer of 11% amount by weight relative to acetone, the temperature of reaction of 110 DEG C and under 28 bar hydrogen pressures, obtains the conversion completely of this acetone.The transformation efficiency of MEoA is 99.7%, and N-(sec.-propyl) thanomin selectivity is 98.5% simultaneously, and namely the thick molar yield of IPAE is 98.2% relative to the MEoA used.
embodiment 4: synthesize N-(normal-butyl) diethanolamine (BDEoA) according to semicontinuous method (C7DEoA type) from butyraldehyde-n and 85%DEoA
Use the butyraldehyde-n/DEoA mol ratio of 1.04, relative to Amperkat SK-NiFeCr 4546 catalyzer of the amount by weight that DEoA is 7.3%, semicontinuous introducing butyraldehyde-n within 1 hour 15 minutes periods, make this temperature of reaction maintain 65 DEG C-70 DEG C simultaneously, under 28 bar hydrogen pressures, obtain the conversion completely of butyraldehyde-n.The transformation efficiency of DEoA is 94%, and N-(normal-butyl) diethanolamine selectivity is 98.3% simultaneously, and therefore the thick molar yield of BDEoA is 92.4% relative to the DEoA used.
By this reacting coarse product of fractionation, extract BDAoE at the pressure of 25 millibars with under the tower top temperature of 145 DEG C-146 DEG C.The purity of BDEoA is 99.2%, and distillation yield is 91% simultaneously.The BDEoA of preparation like this painted lower than 3 Pt-Co units, and is 25 Pt-Co units when leaving distillation after envrionment temperature lucifuge in glass flask stores 18 months.
embodiment 5: synthesize N, N'-bis--(normal-butyl) thanomin (DBEoA) according to semicontinuous method (C7DEoA type) from butyraldehyde-n and MEoA
Use the butyraldehyde/MEoA mol ratio of 2.16, relative to Amperkat SK-NiFeCr 4546 catalyzer that MEoA is 10.6% amount by weight, semicontinuous introducing butyraldehyde within 1 hour 50 minutes periods, make temperature of reaction maintain 70 DEG C simultaneously, under the hydrogen pressure of 28 bar, obtain the conversion completely of butyraldehyde and MEoA.The thick molar yield of DBEoA is relative to the MEoA used 79%; Two kinds of principal by product are N-(normal-butyl) thanomin and propyl carbinol.
By this reacting coarse product of fractionation, extract DBEoA at the pressure of 46 millibars with under the tower top temperature of 130.5 DEG C.The purity of DBEoA is 99.8%, and simultaneously distillation yield is 86% and painted lower than 3 Pt-Co units.
Claims (10)
1. for the preparation of the method for formula (A) alkyl alkanolamine:
Wherein:
R
1represent hydroxyalkyl, wherein moieties is straight chain and comprises two carbon atoms;
R
2be selected from hydrogen atom and comprise two carbon atoms and the straight chained alkyl replaced with one or more hydroxyl (-OH);
R and R', can be same or different, eachly be selected from hydrogen atom, alkyl, hydroxyalkyl, alkoxyl group, alkylamino, dialkyl amido, alkoxyalkyl, wherein alkyl be comprise 1-10 carbon atom based on chain that is linear or branched hydrocarbon, with the cycloalkyl comprising 3-9 carbon atom, qualifications is that R and R' eachly side by side can not represent hydrogen atom;
Or
R with R' jointly formed together with carrying their carbon atom saturated or wholly or in part undersaturated, single-, two-or polycyclic moiety, it optionally comprises one or more heteroatoms being selected from oxygen, sulphur and nitrogen,
Described method is included in the step making formula (1) carbonyl containing compound reduction amination when hydrogen and catalyzer exist with formula (2) hydroxyalkyl amine:
Wherein R, R', R
1and R
2as defined above;
The azanol of its Chinese style (2) uses as an aqueous solution.
2. method according to claim 1, its Chinese style (1) compound is selected from acetone, pyruvic alcohol, methyl ethyl ketone (MEK), methyl propyl ketone, methyl isopropyl Ketone, methyl iso-butyl ketone (MIBK), metacetone, diisobutyl ketone, Tetralone an intermediate of Sertraline, methyl phenyl ketone, p-methyl aceto phenone, p-methoxy-acetophenone, meta-methoxy methyl phenyl ketone, 2-aminoacetophenone, 1-phenyl-3-butanone, cyclobutanone, cyclopentanone, pimelinketone, benzophenone, 2-Uvinul A Plus, 3-Uvinul A Plus, 4-Uvinul A Plus, 3, 3, 5-trimethylcyclohexanone, 2, 6-dimethylcyclohexanon, suberone, cyclododecanone, acetaldehyde, propionic aldehyde, butyraldehyde-n, isobutyric aldehyde, pivalyl aldehyde, valeral, n-hexyl aldehyde, 2-ethyl hexanal, enanthaldehyde, octanal, the undecyl aldehyde, phenyl aldehyde, aubepine, p-tolualdehyde, phenylacetic aldehyde, hydroxy pivalin aldehyde and furfural.
3. method according to claim 1, its Chinese style (2) compound is selected from monoethanolamine and diethanolamine.
4. according to the method for any one of claim 1-3, its Chinese style (A) compound be from methyl ethyl ketone and obtain from monoethanolamine N-the second month in a season-butylethanolamine (sBAE), from enanthaldehyde and N-(n-heptyl) diethanolamine (C7DEoA) that obtains from diethanolamine (DEoA), from acetone and N-(sec.-propyl) thanomin that obtains from monoethanolamine (MEoA), from butyraldehyde-n and N-(normal-butyl) diethanolamine that obtains from diethanolamine (DEoA), with from butyraldehyde-n and the N that obtains from monoethanolamine (MEoA), N'-bis-(normal-butyl) thanomin.
5., according to the method for any one of claim 1-3, be wherein selected from the hydrogenation catalyst of the metal of the 8th, 9,10 and 11 races based on the periodic table of elements (IUPAC) based on described catalyzer.
6., according to the method for any one of claim 1-3, wherein hydrogen pressure is between normal atmosphere to 150 clings to.
7., according to the method for any one of claim 1-3, wherein temperature of reaction is in the scope of 20 DEG C-180 DEG C.
8., according to the method for any one of claim 1-3, it carries out with interval or semicontinuous state.
9., according to the method for any one of claim 1-3, wherein this reacting coarse product is used in distillation procedure.
10., according to the method for any one of claim 1-3, be characterised in that it operates when organic solvent-free.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0954334 | 2009-06-25 | ||
| FR0954334A FR2947265B1 (en) | 2009-06-25 | 2009-06-25 | PROCESS FOR THE PREPARATION OF ALKYLALCANOLAMINES |
| PCT/FR2010/051299 WO2010149936A1 (en) | 2009-06-25 | 2010-06-25 | Process for preparing alkylalkanolamines |
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| CN102459150B true CN102459150B (en) | 2015-03-11 |
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| US (1) | US8916728B2 (en) |
| EP (1) | EP2445863A1 (en) |
| JP (2) | JP5678050B2 (en) |
| KR (1) | KR101379580B1 (en) |
| CN (1) | CN102459150B (en) |
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| CA (1) | CA2765931C (en) |
| FR (1) | FR2947265B1 (en) |
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| BR112014002106A2 (en) * | 2011-07-28 | 2017-06-27 | Angus Chemical | water-based paint or coating |
| CA2874058C (en) * | 2012-07-20 | 2019-10-29 | Koei Chemical Company, Limited | Method for producing 2-(isopropylamino)ethanol |
| EP2784058A1 (en) | 2013-08-15 | 2014-10-01 | Basf Se | Method for improving the colour stability of an ethanol amine |
| JP6414340B2 (en) * | 2016-04-28 | 2018-10-31 | 日本精工株式会社 | Lubricant deterioration detector |
| CN113332979B (en) * | 2021-05-20 | 2022-09-27 | 济南大学 | Preparation method and application of copper catalyst prepared by polymerization reaction |
| CN113402401B (en) * | 2021-06-17 | 2022-05-06 | 福建富润建材科技股份有限公司 | Preparation method of alkanolamine |
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- 2009-06-25 FR FR0954334A patent/FR2947265B1/en not_active Expired - Fee Related
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- 2010-06-25 EP EP10745320A patent/EP2445863A1/en not_active Withdrawn
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| US4190601A (en) * | 1978-05-31 | 1980-02-26 | Union Carbide Corporation | Production of tertiary amines by reductive alkylation |
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| CA2651094A1 (en) * | 2006-05-04 | 2007-11-15 | Basf Se | Neutralized acid group-containing polymers and the use thereof |
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| KR101379580B1 (en) | 2014-04-11 |
| WO2010149936A1 (en) | 2010-12-29 |
| CN102459150A (en) | 2012-05-16 |
| CA2765931A1 (en) | 2010-12-29 |
| JP2015044812A (en) | 2015-03-12 |
| BRPI1011941A2 (en) | 2016-04-26 |
| FR2947265B1 (en) | 2011-08-05 |
| KR20120034112A (en) | 2012-04-09 |
| JP2012530771A (en) | 2012-12-06 |
| US8916728B2 (en) | 2014-12-23 |
| ZA201109439B (en) | 2013-02-27 |
| CA2765931C (en) | 2014-05-20 |
| US20120116126A1 (en) | 2012-05-10 |
| JP5678050B2 (en) | 2015-02-25 |
| EP2445863A1 (en) | 2012-05-02 |
| FR2947265A1 (en) | 2010-12-31 |
| MX2011013735A (en) | 2012-05-08 |
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